Adhesive alpha-olefin inter-polymers

ABSTRACT

The invention relates to novel adhesive alpha-olefin inter-polymers which are largely amorphous and have a rheological behavior that makes them suitable for adhesive use, both without and with minimized amounts of tackifying resins. Specifically, the invention poly-alpha olefin inter-polymer may be composed of A) from 60 to 94 mol % of units derived from one alpha mono-olefin having from 3 to 6 carbon atoms and B) from 6 to 40 mol % of units derived from one or more other mono-olefins having from 4 to 10 carbon atoms and at least one carbon atom more than A); and C) optionally from 0 to 10 mol % of units derived from another copolymerizable unsaturated hydrocarbon, different from A) and B); the diad distribution of component A in the polymer as determined by  13 C NMR as described herein showing a ratio of experimentally determined diad distribution over the calculated Bernoullian diad distribution of less than 1.07; and the storage modulus G′ of said polymer, determined upon cooling as described herein, intersecting a value of 3.10 5  Pa at a temperature of less than 85° C. The invention also describes polymerization processes suitable for the manufacture of these adhesive alpha-olefin inter-polymers.

RELATED APPLICATIONS

The present application is based on Provisional Application Ser. No.60/199,093, filed on Apr. 21, 2000, and on Provisional Application Ser.No. 60/171,715, filed on Dec. 22, 1999.

FIELD OF INVENTION

Adhesive alpha-olefin inter-polymers, adhesive compositions orformulations comprising such inter-polymers for adhesive application andadhesion processes and articles in which adhesive compositions orformulations are used.

BACKGROUND OF INVENTION

Certain alpha-olefin inter-polymers have been used in adhesivecompositions which should yield a significant bond strength afterapplication, show good paper adhesion (e.g. fiber tear on Kraft paper),minimum peel strength of 500 g/cm, low color, low odor, and good thermalstability. For PSA applications, when the substrate is an OPP tape, therolling ball tack test should yield a maximum of 3 cm at ambienttemperature, a S.A.F.T. minimum value of 85° C., a shear (12.5 mm×25 mmarea under a 1 Kg weight) on cardboard at 40° C. of at least 30 hours.Most known alpha-olefin inter-polymers in such compositions have a highmelting point and/or a high crystallinity. These characteristics preventsuch materials, on their own, from being used as an adhesive because anadhesive must a low crystallinity for flexibility and a low plateaumodulus, as well as a low viscosity in many applications. (see J.Adhesion Sci. Technol. Vol 3, No 7 pp551-570 (1989) where an SBSblock-copolymer is used).

In such prior art adhesive formulations, the alpha-olefin inter-polymerscontribute to the bond-strength, but tackifiers are used to increase theTg for good bond strength and bring the high plateau modulus down to anacceptable level by decreasing the polymer chain entanglements. Flowpromoters (waxes etc) are used to improve the flow and ensure wetting ofthe substrate by the formulation. Without tackifiers and flow promoters,such inter-polymers can be used to heat seal at reduced temperatures butare not, generally, regarded as adhesives.

The inter-polymers are derived predominantly from ethylene or propylene(For ethylene based polymers see WO97-15636-A1; WO99/24516; WO9803603(EP-912646) by way of example using single site catalyst; WO97-15636-A1or WO94/10256; U.S. Pat. No. 5,317,070 and WO94/04625, usingsyndiotactic polypropylene as the polymer component, and mentioning onpage 7 line 14 of hexene as comonomer. For propylene based polymersfurther see EP-318049. For basic monomers other than propylene orethylene, see for example EP-422498 a butene-propylene inter-polymerwith up to 20 wt % propylene derived units).

As an example of the inter-polymers used for heat sealing or impactmodification, reference is made to JP62-119212-A2. This discloses arandom copolymer with from 40-90 mole % of propylene, from 10-60 mole %of an alpha-olefin such as butene, hexene, and 4-methylpentene using ametallocene type ethylene-bis tetrahydro-indenyl zirconium dichloride asa catalyst. Similarly JP62-119213-A2 discloses a random copolymer ofbutene (60-98 mole %) with 2-40 mole % of C3-20 alpha-olefin such aspropylene, hexene, and 4-methylpentene.

However, the Examples in JP62-119212-A2 have widely varyingcharacteristics. Example 6 polymerizes propylene and hexene to give 60percent of units derived from propylene and 40 mol % of units derivedfrom hexene. The crystallinity is 26% and the melting point is 123° C.Example 3 uses propylene at 45 mol % with a melting point of 50° C. anda crystallinity 7%. JP62-119212-A2 does not disclose a polymer having acombination of structural characteristics (molecular weight; comonomercontent for example) such that a storage modulus G′ suitable foradhesive applications is reached below 70° C. or providing a low meltingpeak. The polymers are said to have anti-blocking characteristics andare of no use in adhesive applications.

WO99/67307 discloses a terpolymer comprising predominantly propylenederived units for use as films, fibers, and molded articles, and alsoseal layers. The polymers in Table 4 have low comonomer contents, highmelting points and high molecular weights.

WO9920644 discloses elastic composition of propylene homopolymers foradhesive application. Metallocenes are used in the polymerization.

In other documents, alpha-olefin inter-polymers are prepared using aconventional Ziegler-Natta catalyst with a titanium chloride transitionmetal component and an aluminum alkyl activator to give a polymer with amonomer composition in which the amounts of propylene (lower molecularweight comonomer) and higher molecular weight comonomer areapproximately equivalent have been suggested for adhesive application.These have been referred to as A(morphous) P(oly) A(lpha) O(lefin),APAO's for short.

U.S. Pat. No. 3,954,697 discloses in example 1 a propylene-hexene-1copolymer containing 43 mol % of hexene-1 derived units which can becoated onto a tape hot to give a pressure sensitive adhesive material.The polymer may be used without additives (See column 2 lines 34 to 39)and can be applied as a hot melt to a tape without solvent to show PSAbehavior. In U.S. Pat. No. 3,954,697, the amount of hexene deemedessential for a polymer is in excess of 40 mol % and the polymerstructure must be such that that the polymer is entirely amorphous andhas no residual crystallinity (See Column 3 lines 24 to 26) orcrystallinity of a very low order (See column 4 line 8). For example,comparative Example 9 uses 18 mol % hexene in the polymer and obtains amelting point of 145° C. suggesting the absence of Theologicalcharacteristics or melting points associated with satisfactory adhesivebehavior. This polymer lacks tackiness at ambient temperature.

High propylene content APAO with butene comonomer have been made andsold under the Registered trade name Rextac using non-SSC typecatalysts. WO98/42780 discusses the use of such polymers in adhesivecompositions.

More details on such inter-polymers and their use in adhesivecompositions can be found in U.S. Pat. No. 5,478,891. U.S. Pat. No.5,723,546 uses blends to obtain the desired characteristics. Details canbe derived from U.S. Pat. No. 4,217,428, U.S. Pat. No. 4,178,272 andU.S. Pat. No.3954697 which recommend generally high amounts of thehigher molecular weight alpha-olefin comonomer.

WO9823699 and EP 620257 disclose a polymer in which from 70 to 99 mol %is derived from a C6 to C12 alpha-olefin and the remainder is a loweralpha-olefin. The exemplified combinations are of hexene-propylene andoctene-ethylene inter-polymers prepared with a conventionalZiegler-Natta catalyst. A low Tg can be obtained. The material may becross-linked to improve cohesive strength. Nevertheless there aredrawbacks associated with such polymers and their application inadhesive end uses. Such known APAO's are non-homogenous, havesignificant levels of extractables and unsatisfactory physicalproperties, including low cohesive strength, that restrict theapplication and adhesive performance.

SUMMARY OF INVENTION

The invention relates (I) to novel adhesive alpha-olefin inter-polymerswhich are largely amorphous and have a Theological behavior that makesthem suitable for adhesive use. In this aspect, the invention alsorelates to processes for the manufacture of these adhesive alpha-olefininter-polymers.

In one aspect the invention provides a polymer which is suitable foradhesive use and has a sufficiently high storage modulus upon cooling,without relying unduly on the presence of lower molecular weightcomponents such as a tackifier (which can create problems of excessivemigration of its constituents and requires blending) or low molecularimpurities formed in the course of polymerization and/or which has a lowmelting point with a narrow melting range and/or which has a monomerdistribution pattern which provides an improved balance of low meltingpoint and cohesive strength. Therefore in one aspect the inventionprovides an adhesive composition or formulation which contains no or lowamounts of tackifier, yet provides a satisfactory balance of propertiesfor an adhesive composition.

Advantages of the invention include improved polymers which can be usedwith reduced amounts of, or possibly no tackifier, in order to provide ahot melt adhesive composition or formulation. These polymers can be usedwith reduced amounts of, or possibly no solvent, in order to provide aadhesive formulations with reduced environmental impact. Further,another embodiment of the invention provides sprayable adhesiveformulations, including sprayable HMA compositions, comprisingpredominantly of polymers having a reduced plateau modulus and/ormolecular weight.

In one specific embodiment the invention provides in a first aspect apoly-alpha olefin inter-polymer comprising

A) from 60 to 94mol % of units derived from one alpha mono-olefin havingfrom 3 to 6 carbon atoms and

B) from 6 to 40 mol % of units derived from one or more othermono-olefins having from 4 to 10 carbon atoms and at least one carbonatom more than A); and

C) optionally from 0 to 10 mol % of units derived from anothercopolymerizable unsaturated hydrocarbon, different from A) and B);

the diad distribution of component A in the polymer as determined by ¹³CNMR as described herein showing a ratio of experimentally determineddiad distribution over the calculated Bemoullian diad distribution ofless than 1.07; and

the storage modulus G′ of said polymer, determined upon cooling asdescribed herein, intersecting a value of 3.10⁵ Pa at a temperature ofless than 85° C.

In another aspect there is provided a poly-alpha olefin inter-polymerhaving (I)

A) from 60 to 94mol % of units derived from one alpha mono-olefin havingfrom 3 to 6 carbon atoms and

B) from 6 to 40 mol % of units derived from one or more othermono-olefins having from 4 to 10 carbon atoms and at least one carbonatom more than A); and optionally from 0 to 10 mol % of units derivedfrom another copolymerizable unsaturated hydrocarbon, different from A)and B);

the diad distribution of component A in the polymer as determined by ¹³CNMR as described herein showing a ratio of experimentally determineddiad distribution over the calculated Bemoullian diad distribution ofless than 1.07; and

said polymer having a melting behavior as determined by DSC, asdescribed herein, so that T_(m) (interpolymer) is less than 153−2.78×[C_(B+C)] for any given concentration of B) and/or C) components whereT_(m) is the major melting peak of the interpolymer at a given contentof components B) and C) in mol %; [C_(B+C)] is the mol % of component B)plus C).

The invention thus further relates (II) to adhesive compositions whichconsist predominantly of the inter-polymer and to formulations foradhesive end-uses comprising the inter-polymer and in addition limitedamounts of other components such a) tackifiers for lowering the plateaumodulus and/or b) flow promoters such as low molecular weight additivesfor lowering the viscosity of the formulation in its molten state duringthe application of the formulations onto a substrate. Anti-oxidants,stabilisers etc. may also be present in the composition andformulations.

Such compositions or formulations may be a hot melt adhesive (HMA) andbe applied to a substrate in the substantial absence of solvent ordiluent at above ambient temperature to initiate adhesion and then coolto ambient temperature to establish a bond.

Such compositions or formulations may be a pressure sensitive adhesive(PSA) and be applied in the substantial absence of solvent or diluent toa substrate to initiate adhesion at ambient temperature. If the PSA isapplied hot to its substrate to form an article, for example a tape orlabel which is subsequently used at ambient temperature to initiateadhesion, the PSA is known as a hot melt pressure sensitive adhesive(HMPSA).

Such compositions or formulations may be applied as a solution in thepresence of a suitable solvent for the components, to give a solventbased adhesive (SBA). Such solutions are applied to substrate and thesolvent is evaporated. For example, the adhesive layer then actssimilarly to the HMPSA and is called a solvent-based pressure sensitiveadhesive (SBPSA).

The invention additionally relates (III) to processes using suchcompositions or formulations as well as articles obtained by suchprocesses. For example the compositions and formulations of theinvention can be sprayed, preferably in filamentary form, onto asubstrate for use in packaging and for disposable items, such asdiapers, and other sanitary articles or can be used for adhesive tape.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the DSC melting behavior as defined herein for aprior art Rextac RT 2715 grade and a inter-polymer according to theinvention of Example 1;

FIG. 2 illustrates the DSC melting peaks against the comonomer content,for Rextac RT 2715, Examples of the invention herein, and Examples ofJP62-119212-A2 referred to herein

FIG. 3 plots G′ versus the temperature during a progressive coolingcycle according to the method described herein for the polymer ofExample 1 and Example 3;

FIG. 4 represent the obtained NMR graph of the polymer of Example 1 andthe peak assignment is used to calculate the polymer microstructure forthis and other examples.

DETAILED DESCRIPTION OF THE INVENTION

The selection of the monomer contents for the invention inter-polymerscan be combined with the selection of the physical properties to providea polymer which provides an effective polymeric backbone in an adhesiveand requires no or reduced amounts of additional components to achievethe desired balance of processing and adhesive properties. Preferablythen A) is derived from units having from 3 to 6 carbon atoms and ismost preferably propylene; B) is derived from units having from 4 to 10carbon atoms, preferably at least one more carbon atoms than A), and ismost preferably butene-1, hexene-1 or octene-1, and C) is derived fromethylene.

Preferably the polymer is a random copolymer having a statisticallyrandom distribution of component B) and substantially free of blocks ofadjacent one or other of the monomer component B) as determined by NMR.The randomness can be provided in continuous processing by a sufficientlevel of back-mixing in the reactor. In batch processes as used in theexamples herein, a sufficient randomness can be provided by ensuringthat the finishing monomer composition does not vary excessively fromthe initial polymer composition. Suitably any batch reaction should bestopped at a relatively low monomer conversion.

These monomers can be readily polymerized using metallocene basedcatalyst systems to provide low extractability and good adhesivebehavior.

Suitably the inter-polymer contains at least 65 mol % (for goodcrystallinity and bond-strength) and/or no more than 90 mol % of unitsderived from A) to avoid excessive crystallinity and undesirablestiffness. Advantageously the inter-polymer has a crystallinity of atleast 3% and/or no more than 20%, preferably at least 5 mol % and/or nomore than 15% as determined by DSC. Suitably the adhesive composition orformulation as applied as an adhesive has a heat of fusion of from 5 to33 J/g.

The structure and crystallinity of the inter-polymer of the inventionalso influences the melting point. Preferably the inter-polymer has amajor melting peak as determined by DSC of at least 40° C. and/or nomore than 130° C., preferably a melting peak of at least 50° C. and/orno more than 90° C. Low levels of crystallinity should provide theinter-polymer with necessary cohesive strength without significantcompromise of the adhesive performance while the melting behaviordetermines its application temperature.

By selecting an inter-polymer with a suitable Tg, one can also reduce oreliminate the need to blend the polymer with a tackifier. Advantageouslythe inter-polymer has a Tg of at least minus 40° C. and/or no more thanminus 5° C., preferably at least minus 30° C. and/or no more than minus10° C.

The polymer can also be selected by reference to the Theologicalbehavior and preferably has a G′ value of less than 0.3 MPa in atemperature window somewhere between the end-use temperature and theprocessing temperature. With such a low elastic modulus, the adhesiveexhibits high deformability during bond formation, and thus caneffectively wet the substrate to which it is applied. This is aprerequisite to achieve an adhesive bond of sufficient strength.

The inter-polymer of the invention may have any Mw/Mn value as long asthe extractability is low as indicated before. When a metallocene basedcatalyst system is used, the optimum way of achieving the lowextractability is to rely on the narrow Mw/Mn which is advantageouslyfrom 1.5 to 4, especially from 1.8 to 3.5.

As a result of the contribution made by the polymer to the adhesivebehavior of the adhesive composition or formulation, the composition orformulation may be used without relying on solvent, e.g. substantiallyfree of volatile components, and contain no or less than 25 wt % oftackifier, preferably less than 20 wt %. Alternatively the inventionincludes formulating the adhesive in a suitable solvent (SBA).

Depending on the location of the tan δ as determined by rheologymeasurements, the composition may be applied as a HMA, PSA, or SBA.

For optimum use as HMA to be applied by spreading or coating, preferablythe inter-polymer composition or formulation uses an inter-polymerhaving a Melt Index from 1 to 2000 as determined under ASTM D1238method, preferably at least 5, and especially a least 10 and preferablyno more than 1000, and especially no more than 500.

For optimum use as HMA to be applied by spraying, preferably theinter-polymer composition or formulation uses an inter-polymer having aMelt Index flowability of at least 1000.

While the inter-polymer contributes to the adhesive behavior,nevertheless it may be desirable to complement that by relying on otheringredients in the formulation. Optionally then the composition orformulation may further comprise from 1 to 25 wt % of a tackifier and/orfrom 1 to 20 wt % of flow improver.

For optimum use as PSA to be applied by coating, preferably the adhesivecomprises an inter-polymer having a Melt Index from 1 to 5000 asdetermined under ASTM D1238 method preferably 20 to 3000, and especially100 to 2000.

The adhesives containing the inter-polymer may be used in makinghygienic articles containing a structure, elements of which are adheredby a composition or formulation as described above.

In one embodiment, the content of (B) combined with (C) is at least 8mol % and/or less than 40 mol %, and the storage modulus G′ determinedupon cooling as described herein intersects a storage modulus G′ of3×10⁵ Pa at a temperature of less than 70° C.

In one embodiment, the interpolymer has a reactivity ratio R_(A)×R_(B)as determined by NMR as described herein, wherein F_(A) is thereactivity ratio of component (A) over component (B) and R_(B) is theratio of component (B) over component (A), of less than 1.4.

In one embodiment, the interpolymer has a weight average molecularweight as determined by GPC as described herein, of less than 120,000,preferably less than 90,000, and most preferably less than 70,000 and/orat least 20,000, preferably at least 30,000 and especially at least40,000, and the storage modulus G′ of the interpolymer, determined uponcooling as described herein, intersects a storage modulus G′ of 3×10⁵ Paat a temperature of less than 70° C.

In one embodiment, component (A) is derived from units having from 3 to6 carbon atoms and preferably propylene; (B) is derived from unitshaving from 4 to 8 carbon atoms, preferably at least two more carbonatoms than (A), and is preferably butene-1, hexene-1 or octene-1; and(C) is derived from ethylene.

In one embodmiment, the interpolymer includes at least 65 mol %,preferably at least 75 mol % of units derived from (A) and/or no morethan 94 mol %, preferably no more than 90 mol % of (A); at least 6 mol%, preferably at least 10 mol % of (B) and/or no more than 30 mol %,preferably no more than 25 mol % of (B); and/or no more than 5 mol %,most preferably no more than 2 mol % of (C).

In one embodiment, the interpolymer has a heat of fusion of at least 5J/g, preferably at least 10 J/g and/or no more than 40 J/g, preferablyno more than 30 J/g, and most preferably no more than 20 J/g asdetermined by DSC as described herein.

In one embodiment, the interpolymer has a major melting peak asdetermined by DSC, as described herein, of at least 40° C., preferablyof at least 50° C. and/or has a melting point as determined by DSC of nomore than 130° C., preferably no more than 90° C.

In one embodiment, the interpolymer has a Tg determined by DSC, asdescribed herein, of no more than minus 5° C., preferably no more thanminus 15° C., and/or at least minus 40° C., preferably at least minus30° C.

In one embodiment, the interpolymer has a G′ at 120° C. of not greaterthan 1000 Pa, preferably not greater than 500 Pa and most preferably nogreater than 100 Pa.

In one embodiment, the interpolymer has an Mw/Mn as determined by GPC,as described herein, of from 1.5 to 4, more preferably less than 3, mostpreferably less than 2.2 and/or at least 1.6.

In one embodiment, the interpolymer has a storage modulus G′ determinedupon cooling as described herein, intersecting a value of 3×10⁵ Pa at atemperature of less than 85° C.

In one embodiment, the interpolymer has a melting peak as detennined byDSC of at least 40° C., preferably of at least 50° C. and/or has amelting point as determined by DSC of no more than 130° C., preferablyno more than 95° C.

In one embodiment, the interpolymer has a Tg determined by DSC of nomore than minus 5° C., preferably no more than minus 20° C., and/or atleast minus 40° C, preferably at least minus 30° C.

Process of Polymerization

The catalyst selected should generally be suitable for preparingpolymers and copolymers from olefinically, vinylically andacetylenically unsaturated monomers.

In its broadest form the invention can be performed with any SSC (singlesited) catalyst. These generally contain a transition metal of Groups 3to 10 of the Periodic Table; and at least one ancillary ligand thatremains bonded to the transition metal during polymerization. Preferablythe transition metal is used in a reduced cationic state and stabilizedby a cocatalyst or activator. Especially preferred are metallocenes ofGroup 4 of the Periodic table such as titanium, hafnium or zirconiumwhich are used in polymerization in the d⁰ mono-valent cationic stateand have one or two ancillary ligands as described in more detailhereafter. The important features of such catalysts for coordinationpolymerization are the ligand capable of abstraction and that ligandinto which the ethylene (olefinic) group can be inserted.

The metallocene can be used with a cocatalyst, which may be alumoxane,preferably methylalumoxane, having an average degree of oligomerizationof from 4 to 30 as determined by vapor pressure osmometry. Alumoxane maybe modified to provide solubility in linear alkanes but is generallyused from a toluene solution. Such solutions may include unreactedtrialkylaluminum and the alumoxane concentration is generally indicatedby mol Al per liter, which figure includes any trialkyl aluminum whichhas not reacted to form an oligomer. The alumoxane, when used ascocatalyst, is generally used in molar excess, at a mol ratio of from atleast 50 preferably at least 100 and no more than 1000, preferably nomore than 500.

The metallocene may be also be used with a cocatalyst which is a non- orweakly coordinated anion (these term non-coordinating anion as usedherein includes weakly coordinated anions). The coordination should besufficiently weak in any event, as evidenced by the progress ofpolymerization, to permit the insertion of the unsaturated monomercomponent.) The non-coordinating anion may be supplied and reacted withthe metallocene in any of the manners described in the art.

The precursor for the non-coordinating anion may be used with ametallocene supplied in a reduced valency state. The precursor mayundergo a redox reaction . The precursor may be an ion pair of which theprecursor cation is neutralized and/or eliminated in some manner. Theprecursor cation may be an ammonium salt as in EP-277003 and EP-277004.The precursor cation may be a triphenylcarbonium derivative.

The non-coordinating anion can be a halogenated, tetra-aryl-substitutedGroup 10-14 non-carbon, element-based anion, especially those that arehave fluorine groups substituted for hydrogen atoms on the aryl groups,or on alkyl substituents on those aryl groups.

The effective Group 10-14 element cocatalyst complexes of the inventionare, in a preferable embodiment, derived from an ionic salt, comprisinga 4-coordinate Group 10-14 element anionic complex, where A⁻ can berepresented as:

[(M)Q ₁ Q ₂ . . . Q _(i)]⁻,

where M is one or more Group 10-14 metalloid or metal, preferably boronor aluminum, and either each Q is ligand effective for providingelectronic or steric effects rendering [(M′)Q₁Q₂ . . . Q_(n)]⁻ suitableas a non-coordinating anion as that is understood in the art, or asufficient number of Q are such that [(M′)Q₁Q₂ . . . Q_(n)]⁻ as a wholeis an effective non-coordinating or weakly coordinating anion. ExemplaryQ substituents specifically include fluorinated aryl groups, preferablyperfluorinated aryl groups, and include substituted Q groups havingsubstituents additional to the fluorine substitution, such asfluorinated hydrocarbyl groups. Preferred fluorinated aryl groupsinclude phenyl, biphenyl, napthyl and derivatives thereof.

Representative metallocene compounds can have the formula:

L ^(A) L ^(B) L ^(C) _(i) MDE

where, L^(A) is a substituted cyclopentadienyl or heterocyclopentadienylancillary ligand π-bonded to M; L^(B) is a member of the class ofancillary ligands defined for L_(A), or is J, a heteroatom ancillaryligand σ-bonded to M; the L^(A) and L^(B) ligands may be covalentlybridged together through a Group 14 element linking group; L^(c) _(i) isan optional neutral, non-oxidizing ligand having a dative bond to M (iequals 0 to 3); M is a Group 4 or 5 transition metal; and, D and E areindependently monoanionic labile ligands, each having a π-bond to M,optionally bridged to each other or L^(A) or L^(B). The mono-anionicligands are displaceable by a suitable activator to permit insertion ofa polymerizable monomer or macromonomer can insert for coordinationpolymerization on the vacant coordination site of the transition metalcomponent.

Non-limiting representative metallocene compounds includemono-cyclopentadienyl compounds such aspentamethylcyclopentadienyltitanium isopropoxide,pentamethylcyclopentadienyltribenzyl titanium,dimethylsilyltetramethyl-cyclopentadienyl-tert-butylamido titaniumdichloride, pentamethylcyclopentadienyl titanium trimethyl,dimethylsilyltetramethylcyclopentadienyl-tert-butylamido zirconiumdimethyl, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafniumdihydride, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafniumdimethyl, unbridged biscyclopentadienyl compounds such as bis(1,3-butyl,methylcyclopentadienyl) zirconium dimethyl,pentamethylcyclopentadienyl-cyclopentadienyl zirconium dimethyl,(tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdimethyl; bridged bis-cyclopentadienyl compounds such asdimethylsilylbis(tetrahydroindenyl) zirconium dichloride andsilacyclobutyl(tetramethylcyclopentadienyl)(n-propyl-cyclopentadienyl)zirconium dimethyl; bridged bisindenyl compounds such asdimethylsilylbisindenyl zirconium dichloride, dimethylsilylbisindenylhafnium dimethyl, dimethylsilylbis(2-methylbenzindenyl) zirconiumdichloride, dimethylsilylbis(2-methylbenzindenyl) zirconium dimethyl;and fluorenyl ligand-containing compounds, e.g.,diphenylmethyl(fluorenyl)(cyclopentadienyl)zirconium dimethyl; and theadditional mono- and biscyclopentadienyl compounds such as those listedand described in U.S. Pat. Nos. 5,017,714, 5,324,800 and EP-A-0 591 756.All documents are incorporated by reference for purposes of U.S. patentpractice.

Preferred metallocenes include bridged chiral bis cyclopentadienylderivatives which comprise a fused ring system of an indenyl. Suitablythese are substituted in the 2-position relative to the bridge. Mostpreferred are such compounds with no further substitution other thanthat in the 2 position.

Representative non-metallocene transition metal compounds usable asSSC's also include tetrabenzyl zirconium, tetra bis(trimethylsiylmethyl)zirconium, oxotris(trimethlsilylmethyl) vanadium, tetrabenzyl hafnium,tetrabenzyl titanium, bis(hexamethyl disilazido)dimethyl titanium,tris(trimethyl silyl methyl) niobium dichloride,tris(trimethylsilylmethyl) tantalum dichloride.

Additional organometallic transition metal compounds suitable as olefinpolymerization catalysts in accordance with the invention will be any ofthose Group 3-10 that can be converted by ligand abstraction into acatalytically active cation and stabilized in that active electronicstate by a noncoordinating or weakly coordinating anion sufficientlylabile to be displaced by an olefinically unsaturated monomer such asethylene.

Exemplary SSC compounds include those described in the patentliterature. U.S. Pat. No. 5,318,935 describes bridged and unbridgedbisamido transition metal catalyst compounds of Group 4 metals capableof insertion polymerization of α-olefins. International patentpublications WO 96/23010, WO 97/48735 and Gibson, et. al., Chem. Comm.,pp. 849-850 (1998), disclose diimine-based ligands for Group 8-10 metalcompounds shown to be suitable for ionic activation and olefinpolymerization. See also WO 97/48735. Transition metal polymerizationcatalyst systems from Group 5-10 metals wherein the active transitionmetal center is in a high oxidation state and stabilized by lowcoordination number polyanionic ancillary ligand systems are describedin U.S. Pat. No. 5,502,124 and its divisional U.S. Pat. No. 5,504,049.See also the Group 5 organometallic catalyst compounds of U.S. Pat. No.5,851,945 and the tridentate ligand containing Group 5-10 organometalliccatalyst compounds of copending U.S. application Ser. No. 09/302243,filed Apr. 29, 1999, and its equivalent PCT/US99/09306. Bridgedbis(arylamido) Group 4 compounds for olefin polymerization are describedby D. H. McConville, et al, in Organometallics 1995, 14, 5478-5480.Synthesis methods and compound characterization are presented. Furtherwork appearing in D. H. McConville, et al, Macromolecules 1996, 29,5241-5243, described bridged bis(arylamido) Group 4 compounds that areactive catalysts for polymerization of 1-hexene. Additional transitionmetal compounds suitable in accordance with the invention include thosedescribed in WO 96/40805. Cationic Group 3 or Lanthanide metal complexesfor coordination polymerization of olefins is disclosed in copendingU.S. application Ser. No. 09/408050, filed Sept. 29, 1999, and itsequivalent PCT/US99/22690. The precursor metal compounds are stabilizedby a monoanionic bidentate ancillary ligand and two monoanionic ligandsand are capable of activation with the ionic cocatalysts of theinvention. Each of these documents is incorporated by reference for thepurposes of U.S. patent practice.

When using the catalysts of the invention, the total catalyst systemwill generally additionally comprise one or more organometallic compoundas scavenger. Such compounds as used in this application are meant toinclude those compounds effective for removing polar impurities from thereaction environment and for increasing catalyst activity. Impuritiescan be inadvertently introduced with any of the polymerization reactioncomponents, particularly with solvent, monomer and catalyst feed, andadversely affect catalyst activity and stability. It can result indecreasing or even elimination of catalytic activity, particularly whenionizing anion pre-cursors activate the catalyst system. The polarimpurities, or catalyst poisons include water, oxygen, metal impurities,etc. Preferably steps are taken before provision of such into thereaction vessel, for example by chemical treatment or careful separationtechniques after or during the synthesis or preparation of the variouscomponents, but some minor amounts of organometallic compound will stillnormally be used in the polymerization process itself.

Typically these compounds will be organometallic compounds such as theGroup-13 organometallic compounds of U.S. Pat. Nos. 5,153,157, 5,241,025and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132, and that of WO95/07941. Exemplary compounds include triethyl aluminum, triethylborane, triisobutyl aluminum, methylalumoxane, and isobutylaluminumoxane. Those compounds having bulky or C₆-C₂₀ linear hydrocarbylsubstituents covalently bound to the metal or metalloid center beingpreferred to minimize adverse interaction with the active catalyst.Examples include triethylaluminum, but more preferably, bulky compoundssuch as triisobutylaluminum, triisoprenylaluminum, and long-chain linearalkyl-substituted aluminum compounds, such as tri-n-hexylaluminum,tri-n-octylaluminum, or tri-n-dodecylaluminum. When alumoxane is used asactivator, any excess over the amount needed to activate the catalystspresent can act as a poison scavenger compound and additionalorganometallic compounds may not be necessary. Alumoxanes also may beused in scavenging amounts with other means of activation, e.g.,methylalumoxane and triisobutyl-aluminoxane with boron-based activators.The amount of such compounds to be used with catalyst compounds of theinventions is minimized during polymerization reactions to that amounteffective to enhance activity (and with that amount necessary foractivation of the catalyst compounds if used in a dual role) sinceexcess amounts may act as catalyst poisons.

The catalysts may be used advantageously in homogeneous solutionprocesses. Random polymerization in homogeneous conditions furtherpromotes the homogeneity of the resulting polymer. Generally thisinvolves polymerization in a continuous reactor in which the polymerformed and the starting monomer and catalyst materials supplied, areagitated to reduce or avoid concentration gradients. Suitable processesinclude are performed above the melting point of the polymers at highpressure at from 10 to 3000 bar in which the monomer acts as diluent orin solution polymerization using an alkane solvent.

Each of these processes may also be employed in singular, parallel orseries reactors. The liquid processes comprise contacting olefinmonomers with the above described catalyst system in a suitable diluentor solvent and allowing said monomers to react for a sufficient time toproduce the invention copolymers. Hydrocarbyl solvents are suitable,both aliphatic and aromatic, hexane is preferred. Generally speaking,the polymerization reaction temperature can vary from 40° C. to 250° C.Preferably the polymerization reaction temperature will be from 60° C.to 220°. The pressure can vary from about 1 mm Hg to 2500 bar,preferably from 0.1 bar to 1600 bar, most preferably from 1.0 to 500bar.

The process can be carried out in a continuous stirred tank reactor, ormore than one operated in series or parallel. These reactors may have ormay not have internal cooling and the monomer feed my or may not berefrigerated. See the general disclosure of U.S. Pat. No. 5,001,205 forgeneral process conditions. See also, international application WO96/33227 and WO 97/22639. All documents are incorporated by referencefor US purposes for description of polymerization processes, metalloceneselection and useful scavenging compounds.

EXAMPLES

The following Examples are for illustrative purposes only. The Tests andmeasurements used in the claims and the following examples are performedas follows:

Measuring Method I

Dynamic Theological properties were determined with a RMS800 equipmentmanufactured by Rheometric Scientific, Piscataway, N.J. In order tobetter simulate the real-life process where the materials is applied inthe molten state and subsequently cooled down, dynamic moduli wererecorded when decreasing temperature from 120 C. down to −20 C. Theoutput of the test is therefore the evolution of the storage modulus G′,the loss modulus G″, as well as the ratio tan δ=G″/G′ as a function oftemperature. Measurements were made at a constant frequency of 1 Hz,using a 12.5 mm diameter plate-and-plate geometry. In order to performmeasurements at sub-ambient temperatures, liquid nitrogen cooling devicewas used throughout the whole test, which was minimizing at the sametime the risk of thermal-oxidative degradation at high temperature. Inorder to compensate for dimension changes during the experiments(thermal expansion of tools and samples, as well as sample shrinkageduring crystallization) the gap between the two plates wereautomatically adjusted so to keep a slight constant compression force onthe sample. Due to the broad range of mechanical behavior investigated(from the molten state down to the glassy region), the magnitude of thedeformation applied was also adjusted during the test in order to keepthe force level between measurable limits, and remain well within thelinear viscoelastic region at all times.

DSC-peak melting point and crystallinity were determined using aprocedure that described as follows. A predetermined amount of samplepressed at approximately 150° C. to 200° C. to form a film. A centralpiece of the film (preferably 7 to 12 mg) is removed with a punch dieand annealed for 120 hours at room temperature. Thereafter, DSC data wasobtained (TA Instruments 2920 temperature modulated DSC) by cooling thesample at −50° C. and subsequently heating it at 10° C./min to 150° C.where it stays isothermally for 5 min before a second cooling-heatingcycle is applied. Both the first and second cycle thermal events arerecorded. The maximum melting peak is recorded as Tm and the area underthe endothermic transition is used to calculate the crystallinitypercent. The crystallinity percent is calculated using the formula,[area under the curve (Joules/gram)/165 (Joules/gram)]*100.

The NMR methodology was the following. The sample was prepared bydissolving +/−0.5 g of polymer in 2.5 ml of TCB (trichlorobenzene), towhich later 0.5 ml of Deuterobenzene was added. The analysis wasperformed at 300 MHz NMR instrument, at 125 degree C., the acquisitiontime was 2 sec, delay 38 sec, full decoupling, 1024 transients. Thereactivity ratio was determined using the formula 4*PP*HH/(PH+HP)2.Bemouillian behavior implies that there is no influence from the lastcomonomer unit in the growing chain on the next one coming in, thereforeincorporation is only depended on monomer concentration in the feed. Aperfectly Bemouillian system would have a product of reactivity ratiosof r_(a)*r_(b)=1. For example, Rextac (a Ziegler-Natta propylenecopolymer) has a product reactivity ratios of 1.3, polymer in presentinvention between 0.9<r_(a)*r_(b)<1.1. Therefore these polymers are muchmore Bernullian than the Rextac. Polymer Sequence Determination, J. C.Randall, Academic Press 1977.

All molecular weights are weight average molecular weight unlessotherwise noted. Molecular weights (weight average molecular weight (Mw)and number average molecular weight (Mn) were measured by Gel PermeationChromatography, unless otherwise noted, using a Waters 150 GelPermeation Chromatograph equipped with a differential refractive indexdetector and calibrated using polystyrene standards. Samples were run ineither THF (45° C.) or in 1,2,4-trichlorobenzene (145° C.) dependingupon the sample's solubility using three Shodex GPC AT-80 M/S columns inseries. This general technique is discussed in “Liquid Chromatography ofPolymers and Related Materials III'” J. Cazes Ed., Marcel Decker, 1981,page 207, which is incorporated by reference for purposes of U.S. patentpractice herein. No corrections for column spreading were employed;however, data on generally accepted standards, e.g. National Bureau ofStandards Polyethylene 1475, demonstrated a precision with 0.1 units forMw/Mn which was calculated from elution times. The numerical analyseswere performed using Expert Ease software available from WatersCorporation.

Examples of Inter-polymers

The following examples are presented. All parts, proportions andpercentages are by weight unless otherwise indicated. All examples werecarried out in dry, oxygen-free environments and solvents. Although theexamples may be directed to certain embodiments of the presentinvention, they are not to be viewed as limiting the invention in anyspecific respect. The polymers are prepared on a laboratory scale usingbatch reactors with stirring. In these examples certain abbreviationsare used to facilitate the description. These include standard chemicalabbreviations for the elements. Melt Index (MI) values in thedescription and claims were measured according to ASTM D 1238 conditionE at 190° C. with a 2.16 kg. load.

The toluene was further dried over a sodium/potassium alloy.Triethylaluminum was purchased from Akzo Nobel. Elemental Analyses wereperformed by Galbraith Laboratories, Inc.

Preparation of Polymer

Example 1

300 ml of prepurified and degassed hexane was transferred into astainless steel autoclave reactor with internal capacity of 1000 ml. Thereactor had been maintained under slight positive argon atmosphere atall times. Consequently, 2 ml solution of 10% wt. methylaluminoxane intoluene, supplied by Aldrich, was transferred into the autoclave. 40 mlof prepurified hexene was added and the mixture was stirred until stablepressure was reached. The reactor was maintained at a pressure slightlyabove atmospheric. In succession, 50 g of prepurified propylene wasadded under stirring. The reactor mixture was heated to 90° C. At thisreactor temperature premixed 2 mg ofdimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium dichloride (1 mg/1ml of toluene) and 2 ml solution of 10 wt. % methylaluminoxane intoluene were placed in the reactor. The polymerization was conducted for30 minutes. The product which was soluble in hexane was precipitatedtwice in acidified isopropanol. Thereafter, the product was filtered anddried under reduced pressure for 24 hr. The yield was 48 g.

The composition as determined by NMR was 73% mole propylene and 27% molehexene derived units. The molecular weights and molecular weightdistribution from GPC were: Mn=46 k, Mw=93 k, Mz=168 k, Mw/Mn=2.04.

The DSC showed Tm=41° C. this melting point was observed only at thefirst heating (See FIG. 1). This due to the fact that the materialcrystallizes slowly (depending on the material crystallization can takedays or even weeks). The crystallinity during the first heating was6.7%. The glass transition was minus 23° C.

Example 2

The polymerization was conducted in the same way as in Example 1 exceptthat the supplied monomer proportions were changed. 73 g of product wereobtained. From NMR data the composition was 74 mole % propylene and 26mole % hexene. The DSC data showed Tm=43° C., crystallinity 7% andTg=−21° C. The molecular weight information were obtained from GPC(Mw=99 k, Mn=44 k, Mz=160 k, Mw/Mn=2.24).

Example 3

500 ml of purified and degassed toluene was transferred into a stainlesssteel autoclave reactor with internal capacity of 1000 ml. The reactorhad been maintained under slightly positive N₂ atmosphere at all times.Consequently, 1 ml solution of 10% wt. methylaluminoxane in toluene wastransferred into the autoclave. Then, 40 ml of prepurified hexene wasadded and the mixture was stirred until a stable pressure was reached.The reactor was maintained at a positive pressure (i.e. slightly aboveatmospheric). In succession, 150 ml of prepurified liquid propylene wasadded under stirring. The reactor mixture was heated to 95° C. At thisreactor temperature premixed 0.5 mg ofdimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium dichloride (1 mg/1ml of toluene) and 1 ml solution of 10 wt. % methylaluminoxane intoluene were placed in the reactor. The polymerization was conducted for20 minutes. The product which was soluble in hexane was precipitated inslightly acidified isopropanol. Thereafter, the product was filtered,washed and dried under reduced pressure for 24 hr. The yield was 75.8 g.

The composition was determined by NMR (91.9% mole propylene and 8.1%mole hexene). The molecular weights and molecular weight distributionfrom GPC data were: Mn=11 k, Mw=25 k, Mw/Mn=2.2.

The DSC showed Tm=95° C. (melting peak), Tc=50° C. The crystallinity was18%. The glass transition temperature was minus 6° C.

Example 4

The polymerization procedure described in Example 1 was substanciallyfollowed conducted in the same way as in except that the suppliedmonomer proportions were slightly changed, anddimethylsilyl-bis(2-methyl-indenyl)zirconium dichloride (1 mg/1 ml oftoluene) was the used catalyst. The product which was soluble in hexanewas precipitated in isopropanol. Thereafter, the product was filteredand dried under reduced pressure for 24 hr. The yield was 70 g.

The composition was determined by NMR (79% mole propylene and 21% molehexene). The molecular weights and molecular weight distribution fromGPC data were: Mn=14 k, Mw=28 k, Mz=44 k, Mw/Mn=2.0.

The DSC showed Tm=45° C. this melting point was observed only at thefirst heating. The crystallinity during the first heating was 10%. Theglass transition was −22° C.

Example 5

The polymerization was conducted in the same way as in Example 4 exceptthat 60 ml of hexene was introduced into the autoclave and the reactiontemperature was 75° C. Also scavenger, catalyst and cocatalyst supplywere cut to half. 54 g of product were obtained. From NMR data thecomposition was 74 mole % propylene and 26 mole % hexene. The DSC datashowed Tm=42° C., crystallinity 11% and Tg=-23° C. The molecular weightinformation were obtained from GPC (Mw=108 k, Mn=56 k, Mz=171 k,Mw/Mn=1.93).

Example 6

500 ml of purified and degassed toluene was transferred into a stainlesssteel autoclave reactor with internal capacity of 1000 ml. The reactorhad been maintained under slightly positive N₂ atmosphere at all times.Consequently, 1 ml solution of 10% wt. methylaluminoxane in toluene wastransferred into the autoclave. Then, 60 ml of prepurified hexene wasadded and the mixture was stirred until a stable pressure was reached.The reactor was maintained at a positive pressure (i.e. slightly aboveatmospheric). In succession, 100 ml of prepurified liquid propylene wasadded under stirring. The reactor mixture was heated to 60° C. At thisreactor temperature premixed 0.5 mg ofdimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium dichloride (1 mg/1ml of toluene) and 1 ml solution of 10 wt. % methylaluminoxane intoluene were placed in the reactor. The polymerization was conducted for20 minutes. The product which was soluble in hexane was precipitated inslightly acidified isopropanol. Thereafter, the product was filtered,washed and dried under reduced pressure for 24 hr. The yield was 68 g.

The composition was determined by NMR (91% mole propylene and 9% molehexene). The molecular weights and molecular weight distribution fromGPC data were: Mn=55 k, Mw=105 k, Mw/Mn=1.9.

The DSC showed Tm=86° C. (melting peak), Tc=25° C. The crystallinity was15%. The glass transition temperature was minus 8° C.

Example 7

400 ml of purified and degassed hexane was transferred into a stainlesssteel autoclave reactor with internal capacity of 1000 ml. The reactorhad been maintained under slight positive argon atmosphere at all times.Consequently, 1.5 ml solution of 10% wt. methylaluminoxane in toluenewas transferred into the autoclave. 15 ml of purified hexene was addedand the mixture was stirred until stable pressure. The reactor wasmaintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 80° C. At this reactor temperature premixed and sufficientlyaged, 0.8 ml dimethylsilyl-bis(2-methyl-indenyl)zirconium dichloride(mg/ml of toluene) and 1 ml of 10 wt. % methylaluminoxane in toluenewere placed in the reactor. The polymerization was conducted for 10minutes. Threafter, the reactor was cooled down and vented to theatmosphere. The product, which was soluble in hexane, was precipitatedin slightly acidified isopropanol. Thereafter, the product was washed,filtered and dried under reduced pressure for 24 hr. The yield was 20 g.

The composition was determined by NM (93.6% mole propylene/6.4% molehexene).

The DSC showed melting peak at 94° C., crystallization peak at 48° C.The crystallinity was 18%. The glass transition was −12° C.

Example 8

300 ml of purified and degassed hexane was transferred into a stainlesssteel autoclave reactor with internal capacity of 1000 ml. The reactorhad been maintained under slightly positive argon atmosphere at alltimes. Consequently, 1.5 ml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. 15 ml of purified octene wasadded and the mixture was stirred until stable pressure. The reactor wasmaintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 90° C. At this reactor temperature premixed and sufficientlyaged, 0.8 ml dimethylsilyl-bis(2-methyl-indenyl)zirconium dichloridedissolved in 1 ml toluene (1 mg/1 ml) and 1 ml solution of 10 wt. %methylaluminoxane in toluene were placed in the reactor. Thepolymerization was conducted for 15 minutes. Threafter, the reactor wascooled down and vented to the atmosphere. The product, which was solublein hexane, was precipitated in slightly acidified isopropanol.Thereafter, the product was washed, filtered and dried under reducedpressure for 24 hr. The yield was 46 g.

The composition was determined by NMR 93.2% mole propylene/6.8% moleoctene). The molecular weights and molecular weight distribution fromGPC data were: Mn=23 k, Mw=50 k, Mz=91 k, Mw/Mn=2.16.

The DSC showed melting peak at 94° C. The crystallinity was 20%.

Example 9

300 ml of purified and degassed hexane was transferred into a stainlesssteel autoclave reactor with internal capacity of 1000 ml. The reactorhad been maintained under slightly positive argon atmosphere at alltimes. Consequently, 1.5 ml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. 45 ml of purified 1-butenewas added and the mixture was stirred until stable pressure. The reactorwas maintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 85° C. At this reactor temperature premixed and sufficientlyaged, 1 ml dimethylsilyl-bis(2-methyl-indenyl)zirconium dichloridedissolved in 1 ml toluene (1 mg/1 ml) and 1 ml solution of 10 wt. %methylaluminoxane in toluene were placed in the reactor. Thepolymerization was conducted for 30 minutes. Thereafter, the reactor wascooled down and vented to the atmosphere. The product, which was solublein hexane, was precipitated in slightly acidified isopropanol.Thereafter, the product was washed, filtered and dried under reducedpressure for 24 hr. The yield was 51.5 g.

The composition was determined by NMR 90.7% mole propylene 9.3% mole1-butene). The molecular weights and molecular weight distribution fromGPC data were: Mn=24 k, Mw=59 k, Mz=136 k, Mw/Mn=2.5.

The DSC showed melting peak at 110° C. and crystallization peak at 70°C. and Tg at −8° C.

Example 10

400 ml of purified and degassed hexane was transferred into a stainlesssteel autoclave reactor with internal capacity of 1000 ml. The reactorhad been maintained under slightly positive argon atmosphere at alltimes. Consequently, 1.5 ml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. 30 ml of purified 1-butenewas added and the mixture was stirred until stable pressure. The reactorwas maintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 85° C. At this reactor temperature premixed and sufficientlyaged, 0.2 ml dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride dissolved in 1 ml toluene (1 mg/1 ml) and 0.5 ml solution of10 wt. % methylaluminoxane in toluene were placed in the reactor. Thepolymerization was conducted for 15 minutes. Threafter, the reactor wascooled down and vented to the atmosphere. The product, which was solublein hexane, was precipitated in slightly acidified isopropanol.Thereafter, the product was washed, filtered and dried under reducedpressure for 24 hr. The yield was 21.5 g.

The composition was determined by NMR 81.4% mole propylene/18.6% mole1-butene). The molecular weights and molecular weight distribution fromGPC data were: Mn=88 k, Mw=190 k, Mz=318 k, Mw/Mn=2.16.

The DSC showed melting peak at 105° C. crystallization peak at 63° C.The crystallinity was 24% and the Tg was −9° C.

Example 11

400 ml of purified and degassed hexane was transferred into a stainlesssteel autoclave reactor with internal capacity of 1000 ml. The reactorhad been maintained under slightly positive argon atmosphere at alltimes. Consequently, 1.5 ml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. 40 ml of purified 1-butenewas added and the mixture was stirred until stable pressure. The reactorwas maintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 85° C. At this reactor temperature premixed and sufficientlyaged, 0.2 ml dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride dissolved in 1 ml toluene (1 mg/1 ml) and 0.5 ml solution of10 wt. % methylaluminoxane in toluene were placed in the reactor. Thepolymerization was conducted for 15 minutes. Thereafter, the reactor wascooled down and vented to the atmosphere. The product, which was solublein hexane, was precipitated in slightly acidified isopropanol.Thereafter, the product was washed, filtered and dried under reducedpressure for 24 hr. The yield was 40 g.

The composition was determined by NMR 71.4% mole propylene/23.1% moleoctene). The molecular weights and molecular weight distribution fromGPC data were: Mn=88 k, Mw=182 k, Mz=298 k, Mw/Mn=2.06.

The DSC showed melting peak at 96° C. crystallization peak at 52° C. Thecrystallinity was 22% and the Tg was −16° C.

Example 12

400 ml of purified and degassed hexane was transferred into a stainlesssteel autoclave reactor with internal capacity of 1000 ml. The reactorhad been maintained under slightly positive argon atmosphere at alltimes. Consequently, 1.5 ml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. 60 ml of purified 1-butenewas added and the mixture was stirred until stable pressure. The reactorwas maintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 95° C. At this reactor temperature premixed and sufficientlyaged, 1 ml dimethylsilyl-bis(2-methyl-indenyl)zirconium dichloridedissolved in 1 ml toluene (1 mg/1 ml) and 1 ml solution of 10 wt. %methylaluminoxane in toluene and 2 ml of purified hexane were placed inthe reactor. The polymerization was conducted for 15 minutes.Thereafter, the reactor was cooled down and vented to the atmosphere.The product, which was soluble in hexane, was precipitated in slightlyacidified isopropanol. Thereafter, the product was washed, filtered anddried under reduced pressure for 24 hr. The yield was 56.6 g.

The composition was determined by NMR 67.3% mole propylene/26.7% mole1-butene). The molecular weights and molecular weight distribution fromGPC data were: Mn=19 k, Mw=40 k, Mz=70 k, Mw/Mn=2.22.

The DSC showed melting peak at 63° C. crystallization peak at 23° C. Thecrystallinity was 13% and the Tg was −21° C.

Table 1 summarizes the polymerisation conditions and polymercharacteristics of the preceding Examples.

The Table 2 shows the 13C NMR results for the preceding Examples.

Table 3 provides data on the adhesive performance of selected polymersmade as described above in IA application.

Given that the polymers of the invention can be utilized without the useof tackifiers it is likely that they can be applied by spraying.Continuous fiberization techniques involve the fast stretching of a hotmelt filament extruded through a nozzle. Therefore, good flow-ability inthe nozzle itself is required and the ability to maintain a continuousfilament without break is needed. The polymers of the invention have anarrow molecular weight distribution, similar to the polymers alreadyused in sprayable formulations such as triblock styrenic copolymers ormetallocene catalyzed plastomers (EP-858489, WO-9715636). The elasticityin the molten state is reduced, therefore, the occurrence of undesirablehigh stresses in the stretched filament are avoided. In contrary tohighly tackified systems, the substantial absence of low molecularweight species (i.e. tackifiers, plasticizers) in the current inventionprovides a further guarantee of the cohesion of the systems in themolten state, since nearly all molecules are long enough to entanglewith each other. This will further delay the undesired cohesion break ofthe hot melt filament during spraying operations, thereby opening newavenues for even faster line speeds.

The polymers of the invention were also applied from a solvent solutionwith a minor amount of tackifier. An easy release performance was shown,which due to the absence of non-polymeric contaminants indicatessuitability in applications where no residue may be left on the surfaceafter tape removal, such as medical tape.

The polymers of the invention are also intended for use in adhesives,sealing, and coatings. They may be added as hot melts alone or withother components such as tackifiers, antioxidants, crystallinitymodifiers, etc. They may added in a suitable solvent alone or with othercomponents such as tackifiers, antioxidants, crystallinity modifiers,etc. and the solvent is evaporated after application on a substrate.

TABLE 1 Co- Al/Zr Mol % Mw Tm Tg Crystallinity Example TM catalyst molratio C3⁼ Comonomer x[10³] Mw/Mn [° C.] [° C.] X % 1dimethylsilyl-bis(2-methyl-4- MAO 1000 73 Hexene 93 2.0 41 −23 6.7phenylindenyl)zirconium dichloride 2 dimethylsilyl-bis(2-methyl-4- MAO1000 75 Hexene 99 2.2 43 −21 7.0 phenylindenyl)zirconium dichloride 3dimethylsilyl-bis(2-methyl-4- MAO 2000 92 Hexene 25 2.2 95 −6 18phenylindenyl)zirconium dichloride 4 dimethylsilyl-bis(2-methyl- MAO 80079 Hexene 28 2.0 45 −22 10 indenyl)zirconium dichloride 5dimethylsilyl-bis(2-methyl- MAO 800 74 Hexene 108 1.9 42 −23 11indenyl)zirconium dichloride 6 dimethylsilyl-bis(2-methyl-4- MAO 2000 90Hexene 105 1.9 86 −8 15 phenylindenyl)zirconium dichloride 7dimethylsilyl-bis(2-methyl- MAO 1000 94 Hexene 96 2.3 94 −12 18indenyl)zirconium dichloride 8 dimethylsilyl-bis(2-methyl- MAO 1000 93Octene 50 2.2 94 −17 20 indenyl)zirconium dichloride 9dimethylsilyl-bis(2-methyl- MAO 800 90.7 Butene 59 2.5 110 −8 25indenyl)zirconium dichloride 10 dimethylsilyl-bis(2-methyl-4- MAO 500081.4 Butene 190 2.2 105 −9 23 phenylindenyl)zirconium dichloride 11dimethylsilyl-bis(2-methyl-4- MAO 5000 71.4 Butene 180 2.1 96 −16 21phenylindenyl)zirconium dichloride 12 dimethylsilyl-bis(2-methyl- MAO800 67.3 Butene 40 2.2 63 −21 13 indenyl)zirconium dichloride

TABLE 2 Mole fraction Mole fraction of PP PP diad Reactivity of PP diadsdiads (Bernullian, (exp.)/PP ratios example (experimental) calculated)diad (calc.) R_(A) × R_(B) Rextac 0.488 0.454 1.075 1.35 1 0.537 0.5430.989 0.92 2 0.540 0.543 0.995 0.93 3 0.846  .847 0.999 0.85 4 0.6320.627 1.008 1.18 5 0.551 0.546 1.009 1.14 6 0.828 0.829 0.999 0.85 70.877 0.876 1.001 1.13 8 0.870 0.869 1.001 1.12 9 0.823 0.823 1.000 1.0610  0.659 0.662 0.995 0.87 11  0.586  0.5912 1.009 0.85 12  0.538 0.5371.002 1.04

TABLE 3 HMA Evaluation- Polymer applied neat Rextac RT 2715 at. 150° C.Neat Polymer 5 1 2 Viscosity at 180° C. 2280  14800  1920  3030  (mPas)(Brookfield As 8. /Spindle 21) Softening Point (° C.)   109.5   72.5  75  72.5 (Average of 2 Samples) 109.3/109.06 72.3/75.6 74.7/75.9 73.7/72.4(Herzog As 1.) Coating. (° C.) (Acumeter 150 150 150 150 As 1.) PressLamination at . . . 110 (PE)/150 (AL 110 (PE)/150 (AL 110 (PE)/150 (AL110 (PE)/150 (AL (° C.) (PHI Press. 4400 & PP) & PP) & PP) & PP) Psi for30 s.) T - Peel at Roomtemp. on 478 455 480 375 PE. G/cm) (Average of 3Samples.) Adhesion Failure. Adhesion Failure. Adhesion Failure. AdhesionFailure. 410/400/380 450/375/540 T - Peel at Roomtemp. on 397 432 387302 Al. G/cm) (Average of 3 Samples.) Adhesion Failure. AdhesionFailure. Adhesion Failure. Adhesion Failure. 410/400/380 430/450/415 T -Peel at Roomtemp. on 498 542 400 370 PP. G/cm) (Average of 3 Samples.)Adhesion Failure. Adhesion Failure. Adhesion Failure. Adhesion Failure.410/400/380 450/375/540 Hot Shear. (Min)  25  5  26  28 (1″ × ½″ × 1Kg./ 25/28/21 5/6/5 31/29/19 23/29/33 Average of 3 Samples.) S.A.F.T.(°C.)  52  42   48.5  42 (1″ × ½″ × 0.5 Kg./ 51.3/52.9/51.8 42.2/42.8/41.749.2/46.5/49.7 41.7/42.8/42.2 Average of 3 Samples.) Static Shear at 60°C.    4.5  1  3  1 (Min.) (1″ × ½″ × 1 Kg./ 4/5/4 1/1/1 4/3/2 1/1/1Average of 3 Samples.)

What is claim is:
 1. A poly-alpha olefin interpolymer comprisingcomponents: (A) from 60 to 94 mol % of units derived from one alphamono-olefin having from 3 to 6 carbon atoms; (B) from 6 to 40 mol % ofunits derived from one or more other mono-olefins having from 4 to 10carbon atoms and at least one carbon atom more than (A); and (C)optionally from 0 to 10 mol % of units derived from anothercopolymerizable unsaturated hydrocarbon, different from components (A)and (B); wherein (i) the diad distribution of component (A) in theinterpolymer as determined by ¹³C NMR divided by the calculatedBernoullian diad distribution is less than 1.07; and (ii) the storagemodulus G′ of the interpolymer determined on cooling, measured at 1 Hz,intersects 3×10⁵ Pa at an intersection temperature of less than 85° C.2. The interpolymer of claim 1, wherein the interpolymer has a meltingbehavior as determined by DSC such that T_(m) (interpolymer) is lessthan 153−2.78×[C_(B+C)] for any given concentration of (B) and (C)components, wherein T_(m) is the major melting peak of the interpolymerat a given content of components (B) and (C) in mole percent, and[C_(B+C)] is the mole percent of component (B) plus the mole percent ofcomponent (C).
 3. A poly-alpha olefin interpolymer having: (A) from 60to 94 mol % of units derived from one alpha mono-olefin having from 3 to6 carbon atoms; (B) from 6 to 40 mol % of units derived from one or moreother mono-olefins having from 4 to 10 carbon atoms and at least onecarbon atom more than (A); and (C) optionally from 0 to 10 mol % ofunits derived from another copolymerizable unsaturated hydrocarbon,different from components (A) and (B); wherein (i) the diad distributionof component (A) in the interpolymer as determined by ¹³C NMR divided bythe calculated Bernoullian diad distribution is less than 1.07; and (ii)the interpolymer has a melting behavior as determined by DSC such thatT_(m) (interpolymer) is less than 153−2.78×[C_(B+C)] for any givenconcentration of (B) and (C) components, where T_(m) is the majormelting peak of the interpolymer at a given content of components (B)and (C) in mole percent, and [C_(B+C)] is the mole percent of component(B) plus the mole percent of component (C).
 4. The interpolymer of claim3, wherein the interpolymer has a storage modulus G′ determined oncooling, measured at 1 Hz, intersecting 3×10⁵ Pa at an intersectiontemperature of less than 85° C.
 5. The interpolymer of claim 1, 2, or 3,wherein the content of (B) combined with (C) is 8 to 40 mol %, andwherein the intersection temperature is less than 70° C.
 6. Theinterpolymer of claim 1 or 3, wherein the interpolymer has a reactivityratio R_(A)×R_(B) as determined by NMR of less than 1.4, wherein R_(A)is the reactivity ratio of component (A) over component (B), and R_(B)is the ratio of component (B) over component (A).
 7. The interpolymer ofclaim 1 or 3, wherein (A) is derived from units having from 3 to 6carbon atoms; (B) is derived from units having from 4 to 8 carbon atoms;and (C) is derived from ethylene.
 8. The interpolymer of claim 1 or 3,wherein the interpolymer has a melting peak as determined by DSC of atleast 40° C.
 9. The interpolymer of claim 1 or 4, wherein G′ at 120° C.is not greater than 1000 Pa.
 10. The interpolymer of claim 1 or 3,wherein the interpolymer has an Mw/Mn as determined by GPC of 1.5 to 4.11. The interpolymer of claim 1 or 4, wherein the weight averagemolecular weight of the interpolymer as determined by GPC is20,000-120,000, and the intersection temperature is less than 70° C. 12.The interpolymer of claim 11, wherein the weight average molecularweight is 30,000-120,000.
 13. The interpolymer of claim 11, wherein theweight average molecular weight is 30,000-90,000.
 14. The interpolymerof claim 13, wherein the weight average molecular weight is40,000-70,000.
 15. The interpolymer of claim 7, wherein (A) is derivedfrom propylene.
 16. The interpolymer of claim 7, wherein (B) is derivedfrom units having two more carbon atoms than the units of (A).
 17. Theinterpolymer of claim 16, wherein the units of (B) are selected frombutene-1, hexene-1 and octene-1.
 18. The interpolymer of claim 7,wherein (A) is derived from propylene; (B) is derived from units having5-8 carbon atoms; and (C) is derived from ethylene.
 19. The interpolymerof claim 1 or 3, comprising 65-94 mol % of units derived from (A); 6-30mol % of units derived from (B); and 0-5 mol % of units derived from(C).
 20. The interpolymer of claim 19, comprising 75-90 mol % of unitsderived from (A) and 10-25 mol % of units derived from (B).
 21. Theinterpolymer of claim 19, comprising 0-2 mol % of units derived from(C).
 22. The interpolymer of claim 21, comprising 75-90 mol % of unitsderived from (A) and 10-25 mol % of units derived from (B).
 23. Theinterpolymer of claim 1 or 3, wherein the interpolymer has a heat offusion of 5-40 J/g as determined by DSC.
 24. The interpolymer of claim23, wherein the heat of fusion is 5-30 J/g.
 25. The interpolymer ofclaim 23, wherein the heat of fusion is 10-30 J/g.
 26. The interpolymerof claim 25, wherein the heat of fusion is 10-20 J/g.
 27. Theinterpolymer of claim 1 or 3, wherein the interpolymer has a meltingpoint as determined by DSC of 130° C. or less.
 28. The interpolymer ofclaim 26, wherein the melting point is 95° C. or less.
 29. Theinterpolymer of claim 8, wherein the interpolymer has a melting peak asdetermined by DSC of 50° C. or less.
 30. The interpolymer of claim 1 or3, wherein the interpolymer has a Tg determined by DSC of minus 40° C.to minus 5° C.
 31. The interpolymer of claim 30, wherein the Tg is minus40° C. to minus 20° C.
 32. The interpolymer of claim 30, wherein the Tgis minus 30° C. to minus 20° C.
 33. The interpolymer of claim 9, whereinG′ at 120° C. is not greater than 500 Pa.
 34. The interpolymer of claim33, wherein G′ at 120° C. is not greater than 100 Pa.
 35. Theinterpolymer of claim 10, wherein Mw/Mn is 1.5 to
 3. 36. Theinterpolymer of claim 10, wherein Mw/Mn is 1.6 to 2.2.
 37. Theinterpolymer of claim 30, wherein Tg is minus 30° C. to minus 15° C. 38.The interpolymer of claim 27, wherein the melting point is 90° C. orless.
 39. The interpolymer of claim 11, wherein the weight averagemolecular weight is 40,000-120,000.
 40. The interpolymer of claim 11,wherein the weight average molecular weight is 20,000-90,000.
 41. Theinterpolymer of claim 11, wherein the weight average molecular weight is40,000-90,000.
 42. The interpolymer of claims 11, wherein the weightaverage molecular weight is 20,000-70,000.
 43. The interpolymer of claim11, wherein the weight average molecular weight is 30,000-70,000. 44.The interpolymer of claim 23, wherein the heat of fusion is 5-20 J/g.45. The interpolymer of claim 23, wherein the heat of fusion of 10-40J/g.
 46. The interpolymer of claim 10, wherein the Mw/Mn is 1.5 to 2.2.47. The interpolymer of claim 10, wherein the Mw/Mn is 1.6 to
 4. 48. Theinterpolymer of claim 10, wherein the Mw/Mn is 1.6 to 3.